High charge density metalloaluminophosphosilicate molecular sieves

ABSTRACT

A method of making and using a new family of crystalline microporous metalloalumino(gallo)phosphosilicate molecular sieves is disclosed. These molecular sieves have been synthesized and are designated high charge density (HCD) MeAPSOs. These metalloalumino(gallo)phosphosilicates are represented by the empirical formula of: 
       R p+   r A +   m M 2+   w E x PSi y O z    
     where A is an alkali metal such as potassium, R is at least one quaternary ammonium cation such as ethyltrimethylammonium, M is a divalent metal such as Zn and E is a trivalent framework element such as aluminum or gallium. This family of metalloalumino(gallo)phosphosilicate materials is stabilized by combinations of alkali and quaternary ammonium cations, enabling unique, high charge density compositions. The HCD MeAPSO family of materials have catalytic properties for carrying out various hydrocarbon conversion processes and separation properties for separating at least one component.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority from application Ser. No. 15/593,209,filed on May 11, 2017 and issuing as U.S. Pat. No. 10,370,257 on Aug. 6,2019 which claimed priority from Provisional Application No. 62/341,281filed May 25, 2016, the contents of which cited application are herebyincorporated by reference in its entirety.

FIELD OF THE INVENTION

This invention relates to a new family of high charge densitymetalloalumino(gallo)-phosphosilicate-based molecular sieves. They arerepresented by the empirical formula:

R^(p+) _(r)A⁺ _(m)M²⁺ _(w)E_(x)PSi_(y)O_(z)

where A is an alkali metal such as potassium, M is a divalent metal suchas Zn²⁺, R is a least one quaternary ammonium cation such asethyltrimethylammonium and E is a trivalent framework element such asaluminum or gallium. The high charge densitymetalloalumino(gallo)phosphosilicate molecular sieves, designated HCDMeAPSO, often exhibit “Si islands.”

BACKGROUND OF THE INVENTION

Zeolites are crystalline aluminosilicate compositions which aremicroporous and which are formed from corner sharing [AlO_(4/2)]⁻ andSiO_(4/2) tetrahedra. Numerous zeolites, both naturally occurring andsynthetically prepared are used in various industrial processes.Synthetic zeolites are prepared via hydrothermal synthesis employingsuitable sources of Si, Al and structure directing agents (SDAs) such asalkali metals, alkaline earth metals, amines, or organoammonium cations.The structure directing agents reside in the pores of the zeolite andare largely responsible for the particular structure that is ultimatelyformed. These species balance the framework charge associated withaluminum and can also serve as space fillers. Zeolites are characterizedby having pore openings of uniform dimensions, having a significant ionexchange capacity, and being capable of reversibly desorbing an adsorbedphase which is dispersed throughout the internal voids of the crystalwithout significantly displacing any atoms which make up the permanentzeolite crystal structure. Zeolites can be used as catalysts forhydrocarbon conversion reactions, which can take place on outsidesurfaces of the zeolite as well as on internal surfaces within the poresof the zeolite.

In 1982, Wilson et al. developed aluminophosphate molecular sieves, theso-called AlPOs, which are microporous materials that have many of thesame properties of zeolites, but are silica free, composed of[AlO_(4/2)]⁻ and [PO_(4/2)]⁺ tetrahedra (See U.S. Pat. No. 4,319,440).Subsequently, charge was introduced to the neutral aluminophosphateframeworks via the substitution of SiO_(4/2) tetrahedra for [PO_(4/2)]⁺tetrahedra to produce the SAPO molecular sieves (See U.S. Pat. No.4,440,871). Another way to introduce framework charge to neutralaluminophosphates is to substitute [M²⁺O_(4/2)]²⁻ tetrahedra for[AlO_(4/2)]⁻ tetrahedra, which yield the MeAPO molecular sieves (seeU.S. Pat. No. 4,567,029). These MeAPO materials generally showed lowsubstitution levels of M²⁺ for Al³⁺, generally on the order of 10%,while several materials, notably MeAPO-44 exhibited M²⁺ for Al³⁺substitution levels of 40%. Later, MeAPO-50 also showed nearly 40%substitution of M²⁺ for Al³⁺, but these examples of high Me²⁺substitution were few (See ZEOLITES, 1995, 15, 583-590). It isfurthermore possible to introduce framework charge on AlPO-basedmolecular sieves via the introduction both of SiO_(4/2) and[M²⁺O_(4/2)]²⁻ tetrahedra to the framework, giving MeAPSO molecularsieves (See U.S. Pat. No. 4,973,785).

Before the SAPO materials of U.S. Pat. No. 4,440,871 were known, therewere attempts to make “phosphate zeolites,” i.e., substitution ofphosphorus for silicon in an aluminosilicate. Such a substitution in analuminosilicate zeolite, [PO_(4/2)]⁺ for [SiO_(4/2)], represents areduction of the negative charge on an aluminosilicate framework. Theinitial work by Flanigen and Grose co-precipitated the components ofsilicoaluminophosphate gels, isolated the resulting solid, suspended theresulting solids in alkali hydroxide solutions and treated them underhydrothermal conditions, yielding a series of phosphate zeolites,including those of LTL, CHA, LTA, and GIS topologies (See E. M. Flanigenand R. W. Grose, ADVANCES IN CHEMISTRY Series No. 101, ACS, WashingtonD. C., 1971). The low phosphate preparations, P/Al≤1.1, resulted inalkali silicoaluminophosphate species that were not as thermally stableas their aluminosilicate analogs, often less than 350° to 400° C., andreduced adsorption capacity in some cases suggest the possibility ofsome occluded phosphate in pores and cages. Similarly, Wacks et al.disclose a process for preparing silicoaluminophosphate zeolites thatentails digesting hydrated aluminophosphate solids in the presence ofsodium silicate solutions to make the desired silicoaluminophosphatematerials, in which the claimed range of phosphate incorporation wasgiven by P₂O₅/Al₂O₃=0-0.2, suggesting that Al/P≥5 in these materials(See K. Wacks et al., U.S. Pat. No. 3,443,892). While eight examples ofthis zeolite synthesis process are disclosed in U.S. Pat. No. 3,443,892,there is no data offered that shows that any P was actually incorporatedinto the zeolite product; a possibility given the claimed range extendsto zero. Many attempts to make silicoaluminophosphate zeolites resembledreactions that would be used to make aluminosilicate zeolites, butcarried out in the presence of phosphate, yielding little phosphateincorporation. Kuhl conducted syntheses of silicoaluminophosphatecompositions, employing high levels of both phosphate and hydroxide,utilizing a combination of tetramethylammonium and sodium hydroxides forthe latter, to make the LTA-related species ZK-21 and ZK-22 (See G. H.Kuhl, INORGANIC CHEMISTRY, 10, 1971, p. 2488). These species exhibit lowphosphate incorporation, Al/P>8.9, and it was concluded that thephosphate was occluded in zeolitic cages rather than incorporated intothe framework. Casci et al. disclose low phosphate chabazite materialsin which the framework phosphorus is claimed to be between 0.05-5 mole%, i.e., P/(Al+Si+P)=0.0005−0.05 (See US 2014/0193327). The amount ofphosphate employed in the reaction mixtures of the examples is low(Al/P>5.5) and no data is offered in the examples to show what the Pincorporation actually is. An outlier disclosed in the SAPO patent (U.S.Pat. No. 4,440,871) uses some sodium aluminate, tetramethylammoniumhydroxide and low phosphate (P/Al=0.4) to prepare SAPO-42 (Example 48),which has the LTA topology and a composition similar to that of ZK-21and ZK-22 mentioned above as Al/P>10. The SAPO-42 product is describedin the application by an essential formulation that does not includealkali, since U.S. Pat. No. 4,440,871 only covers compositions of theformulation mR:(Si_(x)Al_(y)P_(z))O₂. This patent application alsodiscloses the synthesis of SAPO-20 from the same reaction mixturetreated at higher temperature (Example 28). The SAPO-20 product, whichhas the SOD topology, is not porous, but has a slightly enhanced Pcontent as Al/P=3.17. For many years now, a large gap has been presentin the known compositions of microporous silicoaluminophosphates,between the SAPOs disclosed in U.S. Pat. No. 4,440,871 and what areessentially the “phosphate zeolites” reviewed above. In particular, thematerials of intermediate silicon and phosphorus levels are missing.These are materials of intermediate charge density, of higher chargedensity than the SAPOs originating from low level substitution of Siinto neutral AlPO frameworks, but lower charge density than thephosphate zeolites.

A similar charge density gap exists for MeAPO-based materials. In theearly 1990's, high charge density Me²⁺-P—O based molecular sieves,similar to the MeAPOs of U.S. Pat. No. 4,567,029 but without the Al,were developed by Bedard (See U.S. Pat. No. 5,126,120) and Gier (SeeU.S. Pat. No. 5,152,972). These metal phosphates (sometimes arsenates,vanadates) were based on M²⁺ (M=Zn, Co), the general formula of which,in terms of the T-atoms, T²⁺- T⁵⁺, was approximately A⁺T²⁺T⁵⁺O₄, havingframework charge densities similar to Si/Al=1 zeolites and were chargebalanced by alkali cations, A⁺, in the pores. Later attempts to preparemetallophosphates of similar compositions but with organic SDAs led toporous, but interrupted structures, i.e., the structures containedterminal P—O—H and Zn—N bonds (See J. MATER. CHEM., 1992, 2(11),1127-1134). Attempts at Al substitution in a zincophosphate network wascarried out in the presence of both alkali and quaternary ammoniumagents, specifically the most highly charged quaternary ammoniumspecies, tetramethylammonium, but because of the high framework chargedensity, only the alkali made it into the pores to balance frameworkcharge (See U.S. Pat. No. 5,302,362). Similarly, in a high chargedensity zincophosphate system that yielded the zinc phosphate analog ofzeolite X, the synthesis in the presence of Na⁺ and TMA⁺ yielded aproduct that contained considerably less TMA⁺ than Na⁺ (See CHEM.MATER., 1991, 3, 27-29).

To bridge the rather large charge density gap between the MeAPOs of U.S.Pat. No. 4,567,029 and the aforementioned alkali-stabilizedMe²⁺-phosphates of Bedard and Gier, Stucky's group developed a synthesisroute using amines, often diamines in ethylene glycol. They were able tomake high charge density, small pore MeAPOs in which the concentrationsof Co²⁺ and Al³⁺ in R(Co_(x)Al_(1-x))PO₄ were varied such that0.33≤x≤0.9 in the so-called ACP series of materials, the aluminum cobaltphosphates (See NATURE, 1997, 388, 735). Continuing with this synthesismethodology utilizing ethylene glycol reaction mixtures and matching theamines to framework charge densities for R(M²⁺ _(x)Al_(1-x))PO₄ suchthat 0.4≤x≤0.5, (M²⁺=Mg²⁺, Mn²⁺, Zn²⁺, Co²⁺), the large pore materialsUCSB-6, -8 and -10 were isolated (See Science, 1997, 278, 2080).Similarly, this approach also yielded MeAPO analogs of zeolite rho ofthe composition where RM²⁺ _(0.5)Al_(0.5)PO₄, where R=N,N′-diisopropyl-1, 3-propanediamine N²⁺=Mg²⁺Co²⁺ and Mn²⁺. Cowleyfollowed this ethylene glycol-based approach, which he described as“predominantly non-aqueous solvothermal conditions” to synthesize a highcharge density CoGaPO-5, (DABCO)₂[Co₄Ga₅P₉O₃₆], with the DABCO SDA (SeeZEOLITES, 1997, 18, 176-181). Cowley also utilized this strategy toprepare cobalt and zinc gallium phosphates using quinuclidine as theSDA, one of which has the CGS topology with a framework charge densityof −0.125/T-atom (See MICROPOROUS AND MESOPOROUS MATERIALS 1999, 28,163-172). Similarly, Lin and Wang used 1,2 diaminocyclohexane (DACH)with the ethylene glycol approach to prepare a Zn—Ga phosphate of CGStopology with higher Zn incorporation than the Cowley work, realizing aframework charge density of −0.25/T-atom for (H₂DACH)Zn₂Ga₂(PO₄)₄ (SeeCHEMISTRY OF MATERIALS, 2000, 12, 3617-3623). The reliance of thisnon-aqueous synthesis approach on ethylene glycol solvent does not lenditself well to industrial scale, from both a safety and environmentalpoint of view. This non-aqueous approach also leads to very largecrystals, often with dimensions of hundreds of microns, which are toolarge for industrial use, where μ-sized or smaller crystals are oftenpreferred (See SCIENCE, 1997, 278, 2080). Other than this work citedhere, there has been little activity in this intermediate charge densityregion, where 0.2≤x≤0.9 for the [M²⁺ _(x)Al_(1-x)PO₄]^(x−) compositions.

Pursuing aqueous chemistry, Wright used highly charged triquaternaryammonium SDAs to make new MeAPO materials (See CHEM. MATER., 1999, 11,2456-2462). One of these materials, STA-5 with the BPH topology,(Mg_(2.1)Al_(11.9)P₁₄O₂₈), exhibited significant substitution of Mg²⁺for Al³⁺, up to about 15%, but less substitution than seen in Stucky'snon-aqueous ethylene glycol approach.

Unlike the SAPO and MeAPO chemistry discussed in the previousparagraphs, there has been far less investigation in the MeAPSOcompositional arena, perhaps because of the complicated nature of this4-component class of materials. The MeAPO and SAPO materials alreadyconsist of 3 T-atom components derived from substitution of Me²⁺ or Siinto AlPO-based frameworks, respectively. In the prior art, the additionof the fourth T-atom component, either Si or Me²⁺, has generally been aperturbation of an existing MeAPO or SAPO material. Flanigen et al.review aluminophosphate molecular sieves and the periodic table anddiscuss the elements that may be substituted into AlPO-based frameworksalong with the elements that have been incorporated in 22 differentAlPO-based topologies (See Y. Murakami, A. Lijima, J. W. Ward (Eds.),Proc. of 7^(th) Int. Zeolite Conf, (Elsevier Amsterdam 1986), p.103-112). In each case where a MeAPSO composition exists, there is alsoan AlPO, SAPO, or MeAPO composition except for MeAPSO-46, which wasactually found first as a MeAPSO composition, but later found in a MeAPOcomposition with the same SDA, di-isopropylamine (See J. CHEM. SOC.,Faraday Trans., 1993, 89, 4141-4147). There are many examples of MeAPSOcompositions that are derivatives of previously known MeAPO or SAPOcompositions, for instance MeAPSO-34, the derivatives often prepared tosee the effects on catalytic and other material properties (See APPLIEDCATALYSIS A, General 2011 406, 59-62). The MeAPSO compositions, however,have not been the focus of new exploratory synthesis. For instance, theattempts to make higher charge density metalloaluminophosphates byStucky, Cowley and others discussed above have not been extended toMeAPSO compositions. Hence, more than the MeAPOs and SAPOs discussedabove, there is a lack of MeAPSO compositions of intermediate to highcharge density, in other words, MeAPSOs that contain significant amountsof Me²⁺, Si⁴⁺, or both, above the minor to modest substitution levelsdescribed in U.S. Pat. No. 4,973,785. In short, the compositions ofMeAPSO materials have not progressed from what was disclosed in U.S.Pat. No. 4,973,785.

More recently, Lewis et al. developed aqueous solution chemistry leadingto higher charge density SAPO, MeAPO, and MeAPSO materials, enablinggreater substitution of SiO_(4/2) and [M²⁺O_(4/2)]²⁻ into the frameworkfor [PO_(4/2)]⁺ and [AlO_(4/2)]⁻, respectively, using theethyltrimethylammonium (ETMA⁺) and diethyldimethylammonium (DEDMA⁺)SDAs. These materials include MeAPO, SAPO, and MeAPSO versions ofZnAPO-57 (U.S. Pat. No. 8,871,178), ZnAPO-59 (U.S. Pat. No. 8,871,177)and ZnAPO-67 (U.S. Pat. No. 8,697,927), as well as the species MeAPSO-64of BPH topology (U.S. Pat. No. 8,696,886), which was not realized as aMeAPO or SAPO composition with these SDAs. The relationship between theincreasing product framework charge densities and reaction parameters,namely the ETMAOH(DEDMAOH)/H₃PO₄ ratios, were outlined in the literature(See MICROPOROUS AND MESOPOROUS MATERIALS, 189, 2014, 49-63).

Applicants have now synthesized a new family of high charge densitymetalloalumino(gallo)phosphosilicate framework molecular sieves. Thesematerials exhibit higher charge densities than the MeAPSOs mentioned inU.S. Pat. No. 4,973,785, most notably containing either more Me²⁺, moreSi⁴⁺ or both. The high charge density (HCD) MeAPSOs of this inventionare synthesized in a mixed quaternary ammonium/alkali SDA system, forexample ETMA⁺/K⁺. The utilization of alkali in AlPO-based systems isuncommon and is required here to achieve the higher charge density andhigher Me²⁺ and Si⁴⁺ incorporation. The MeAPSO materials of thisinvention are crystalline microporous compositions and often contain “Siislands,” regions of “Si—O—Si” bonding.

SUMMARY OF THE INVENTION

As stated, the present invention relates to a new family ofmetalloalumino(gallo)phosphosilicate molecular sieves designated highcharge density (HCD) MeAPSO. Accordingly, one embodiment of theinvention is a crystalline microporous material having athree-dimensional framework of [MO_(4/2)]²⁻, [EO_(4/2)]⁻, [PO_(4/2)]⁺and SiO_(4/2) tetrahedral units and an empirical composition in the assynthesized form and on an anhydrous basis expressed by an empiricalformula of:

R^(p+) _(r)A⁺ _(m)M²⁺ _(w)E_(x)PSi_(y)O_(z)

where R is at least one of any quaternary ammonium cation, diquaternaryammonium cation triquaternary ammonium cation, quatroquaternary ammoniumcation and mixtures thereof, “r” is the mole ratio of R to P and has avalue of about 0.04 to about 4.0, “p” is the weighted average valence ofR and varies from 1 to 4, A is an alkali metal such as Li⁺, Na⁺, K⁺, Rb⁺and Cs⁺ and mixtures thereof, “m” is the mole ratio of A to P and variesfrom 0.04 to 4.0, M is a divalent metal selected from the group Zn, Co,Mg, Mn and mixtures thereof, “w” is the mole ratio of M to P and variesfrom 0.00268 to 1.35, E is a trivalent element selected from the groupconsisting of aluminum and gallium and mixtures thereof, “x” is the moleratio of E to P and varies from 0.1 to 4.0, “y” is the mole ratio of Sito P and varies from 0.008 to about 4.5, and “z” is the mole ratio of 0to P and has a value determined by the equation:

z=(m+p·r+2·w+3·x+5+4·y)/2

and the crystalline material is characterized by a specific powder x-raydiffraction pattern.

Another embodiment of the invention is a process for preparing thecrystalline metalloalumino(gallo)phosphosilicate molecular sievedescribed above. The process comprises forming a reaction mixturecontaining reactive sources of R, E, P, M, A and Si, and heating thereaction mixture at a temperature of about 60° C. to about 200° C. for atime sufficient to form the molecular sieve, the reaction mixture havinga composition expressed in terms of mole ratios of the oxides of:

aR_(2/p)O:bA₂O:cMO:E₂O₃ :dP₂O₅ :eSiO₂ :fH₂O

where “a” has a value of about 2.1 to about 120, “b” has a value ofabout 0.1 to about 8, “c” has a value of about 0.01 to about 8, “d” hasa value of about 1.69 to about 30, “e” has a value from 0.01 to about 16and “f” has a value from 50 to about 5000.

Yet another embodiment of the invention is a hydrocarbon conversionprocess using the above-described molecular sieve as a catalyst. Theprocess comprises contacting at least one hydrocarbon with the molecularsieve at conversion conditions to generate at least one convertedhydrocarbon.

Still another embodiment of the invention is a separation process usingthe crystalline HCD MeAPSO material. The process may involve separatingmixtures of molecular species or removing contaminants by contacting afluid with the HCD MeAPSO molecular sieve. Separation of molecularspecies can be based either on the molecular size (kinetic diameter) oron the degree of polarity of the molecular species. Removingcontaminants may be by ion exchange with the molecular sieve.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a quaternary phase diagram of the mole fractions of theM²⁺, Al(Ga), Si and P in the molecular sieves of this invention.

FIG. 2 shows the quaternary phase diagram with the fractionalcoordinates of the vertices that define the polyhedral MeAPSOcomposition space.

FIG. 3 shows the 8-vertex polyhedron with the 10 planes that serve asboundaries for the MeAPSO compositional space of this invention alongwith the equations of each of those planes.

DETAILED DESCRIPTION OF THE INVENTION

Applicants have prepared a family ofmetalloalumino(gallo)phosphosilicate-based molecular sieves designatedHCD MeAPSO. Compared to other MeAPSO materials in the prior art, the HCDMeAPSO family of materials contains much more Si or more M²⁺ or both andexhibits high framework (FW) charge densities that require the use ofalkali cations in addition to quaternary ammonium ions to balance the FWcharge. Traditional MeAPSOs, such as those disclosed in U.S. Pat. No.4,973,785 chiefly use organic-based species for FW charge balance, mostoften amines, while the use of alkali is avoided. The instantcrystalline microporous HCD MeAPSO material has an empirical compositionin the as-synthesized form and on an anhydrous basis expressed by theempirical formula:

R^(p+) _(r)A⁺ _(m)M²⁺ _(w)E_(x)PSi_(y)O_(z)

where A is at least one alkali cation and is selected from the group ofalkali metals. Specific examples of the A cations include but are notlimited to lithium, sodium, potassium, rubidium, cesium and mixturesthereof. R is at least one of any quaternary ammonium cation,diquaternary ammonium cation, triquaternary ammonium cation,quatroquaternary ammonium cation and mixtures thereof and “r” is themole ratio of R to P and varies from about 0.04 to about 4.0, while “p”is the weighted average valence of R and varies from about 1 to 4. M andE are tetrahedrally coordinated and in the framework, M is a divalentelement selected from the group of Zn, Mg, Co, Mn and mixtures thereof,while E is a trivalent element selected from aluminum and gallium andmixtures thereof. The value of “m” is the mole ratio of A to P andvaries from 0.1 to about 4.0, “w” is the mole ratio of M to P and variesfrom 0.00268 to 1.35, “x” is mole ratio of E to P and varies from 0.1 toabout 4.0. The ratio of silicon to P is represented by “y” which variesfrom about 0.008 to about 4.5. Lastly, “z” is the mole ratio of 0 to Eand is given by the equation:

z=(m+p·r+2·w+3·x+5+4·y)/2.

When only one type of R quaternary ammonium cation is present, then theweighted average valence is just the valence of that cation, e.g., +1 or+2. When more than one R cation is present, the total amount of R isgiven by the equation:

R_(r) ^(p÷)=R_(r1) ^((p1)+)+R_(r2) ^((p2)+)+R_(r3) ^((p3)+)+ . . .

the weighted average valence “p” is given by:

$p = \frac{{r\; {1 \cdot p}\; 1} + {r\; {2 \cdot p}\; 2} + {r\; {3 \cdot p}\; 3} + \ldots}{{r\; 1} + {r\; 2} + {r\; 3} + \ldots}$

The T-atom compositions comprising this invention, those consisting ofM²⁺, Al(Ga), Si and P, are further constrained and are represented in aquaternary phase diagram, as shown in FIG. 1. Expressing the T-atomcompositions (M²⁺ _(w′)Al_(x′)Si_(y′)P_(z′)) in terms of mole fractions,where w′ is the mole fraction of M²⁺, x′ is the mole fraction of E (Al,Ga), y′ the mole fraction of Si, z′ is the mole fraction of P andw′+x′+y′+z′=1, the mole fractions can be plotted in the quaternary phasediagram of FIG. 1. Illustrating by example, the empirical composition ofthe MeAPSO with M shown as Me in FIG. 1.DEDMA_(0.30)K_(0.24)Zn_(0.52)Al_(0.54)Si_(0.52)P would have molefraction coordinates w′, x′, y′, and z′ given by:

w′(M²⁺)=0.52(M²⁺)/(0.52(M²⁺)+0.54(Al)+0.52(Si)+1(P))=0.20

x′(Al)=0.54(Al)/(0.52(M²⁺)+0.54(Al)+0.52(Si)+1(P))=0.21

y′(Si)=0.52(Si)/(0.52(M²⁺)+0.54(Al)+0.52(Si)+1(P))=0.20

z′(P)=1(P)/(0.52(M²⁺)+0.54(Al)+0.52(Si)+1(P))=0.39.

In the quaternary phase diagram shown in FIG. 1, the mole fraction ofeach T-atom at its labeled vertex is 1 and at the other 3 vertices ofthe tetrahedron the value of the mole fraction of that T-atom is 0 andthe mole fraction varies continuously from 0 to 1 between the threeunlabeled (other) and the labeled vertex. By way of illustration, inFIG. 1, at the vertex labeled Al, the mole fraction of Al is 1, while atthe vertices labeled P, Me²⁺ and Si, the mole fraction of Al is 0. Inthis phase diagram, the coordinates plotted were w′(M²⁺), x′(Al) andz′(P), which uniquely describe the quaternary composition sincey′(Si)=1−(w′+x′+z′). One can thus consider the Si vertex to be theorigin and move along the axes using the given x′, w′, and z′coordinates to find the indicated composition. Using our example abovefor DEDMA_(0.30)K_(0.24)Zn_(0.52)Al_(0.54)Si_(0.52)P, we plot the molefraction coordinates (x′, w′, z′)=(0.21, 0.20, 0.39) by moving theappropriate distance along the x′(Al), w′(M²⁺) and z′(P) axes. FIG. 1shows an 8-vertex polyhedron bounded by 10 planes within the quaternaryphase diagram space and beside it a close-up of the polyhedron. Withinthese boundaries are the claimed MeAPSO compositions of the presentinvention. FIG. 2 shows the quaternary phase diagram with the fractionalcoordinates of the vertices that define the polyhedral MeAPSOcomposition space. These are given below in Table A:

TABLE A Vertex Coordinates of MeAPSO Polyhedron Vertex x′ (Al) w′(Me²⁺)z′(P) 1 0.18499 0.00105 0.14799 2 0.42061 0.00105 0.10515 3 0.496370.00105 0.12409 4 0.48968 0.00105 0.39174 5 0.39841 0.09960 0.49800 60.47801 0.11952 0.39841 7 0.04980 0.44821 0.49801 8 0.05976 0.537850.39841

FIG. 3 shows the 8-vertex polyhedron with the 10 planes that serve asboundaries for the MeAPSO compositional space of this invention alongwith the equations of each of those planes. The compositions that arewithin the boundaries satisfy the following ten inequalities related tothe equations of the planes, basically indicating on which side of theplane that the desired compositions reside as shown in Table B:

TABLE B MeAPSO Compositions - Criteria for x′, w′ and z′ Plane VerticesPlane Equation/Inequalities 1, 2, 3 ,4 w′ ≥ 0.001502 5, 6, 7, 8 x′ +w′ + z′ ≤ 0.996016 4, 5, 6 1.239*x′ + 0.065*w′ + 1.004*z′ ≤ 1 1, 4, 5x′ + 2.274*w′ − 1.25*z′ ≥ 0 1, 5, 7 18.471*x′ + 18.471*w′ − 16.463*z′ ≥1 1, 7, 8 4.599*x′ + 0.6046*w′ + 1.004*z′ ≥ 1 1, 2, 8 1.004*x′ −2.341*w′ + 5.519*z′ ≥ 1 2, 3, 8 x′ + 2.86*w′ − 4.00*z′ ≤ 0 3, 4, 610.009*x′ + 0.9653*w′ + 0.2502*z′ ≤ 5 3, 6, 8 2.212*x′ + 2.212*w′ −0.808*z′ ≤ 1

The HCD MeAPSOs of this invention are crystalline microporous materialswith well-defined pore channels. By “microporous” it is meant that thecrystalline HCD MeAPSO contains at least one pore system with at leastan 8-member ring opening, where an 8-member ring refers to a pore inwhich 8 T-atoms line the pore circumference; this nomenclature iswell-known in the art. That is, themetalloalumino(gallo)phosphosilicates of this invention will exhibit atleast one pore with, for example, 8-ring, 10-ring, 12-ring or an evenhigher number of T-atoms lining the circumference of the pore walls. Onthe other hand, materials that contain 6-rings are not considered to beporous and are not part of this invention, for example, materials of theSOD topology. When the topology of the HCD MeAPSO is known, asidentified by powder x-ray diffraction, the determination ofmicroporosity can be made by consulting the Database of Zeolitestructures at (http://izasc.biw.kuleuven.be/fmi/xsl/IZA-SC/ft.xsl).However, when the topology of the HCD MeAPSOs of this invention is notknown, the determination of microporosity can be made by demonstratingion-exchange of either the as-synthesized or calcinedmetalloalumino(gallo)phosphosilicate without significant structuralchange or by the adsorption of at least a small molecule, such as water,carbon dioxide or n-butane. These practices are well known in the art.

The HCD MeAPSO of this invention is characterized by a high chargedensity compared to that known for most MeAPSO materials and can exhibitsignificant formation of “Si islands,” i.e., Si—O—Si bonding. The FWcharge on ideal HCD MeAPSOs in terms of the empirical formula givenabove is −2·“w”−“x”+1 or −2·M−Al+P. The charge on these materials issuch that highly charged alkali cations are employed in addition toquaternary ammonium cations to balance the FW charge. Comparing MeAPSOmaterials to AlPO materials, two substitution mechanisms leading to FWcharge are at work compared to the parent neutral AlPO materials, namely[M²⁺O_(4/2)]²⁻ for [AlO_(4/2)]⁻ and [SiO_(4/2)] for [PO_(4/2)]⁺. “Si”incorporation is observed in two different ways in the HCD MeAPSOmaterials. In one case, Si only substitutes for P, adding FW charge inthe process as mentioned above. All FW phosphorous must be isolatedbecause it can only be bonded to M or E in the framework via P—O-E(M)bonding, and therefore, the Si substituting for P is also isolated.However, unlike P, Si can also bond to itself through Si—O—Si bonding,forming what are known as “Si islands.” “Si islands” are known in theart even for lower charge density materials, for example, for SAPO-56(See Microporous and Mesoporous Materials, 28, (1999), 125-137). In thepresent case of ideal HCD MeAPSOs, the presence of “Si islands” isapparent when, in terms of the empirical formula describing the HCDMeAPSO, “w”+“x”<1+“y”.

It has also been noted that in the HCD MeAPSO materials that a portionof M²⁺ may also reside in the pores, likely in a charge balancing role.

The crystalline microporous metalloalumino(gallo)phosphosilicate, a HCDMeAPSO, is prepared by a hydrothermal crystallization of a reactionmixture prepared by combining reactive sources of R, A, E, phosphorous,M and silicon. A preferred form of the HCD MeAPSO materials is when E isAl. The sources of aluminum include but are not limited to aluminumalkoxides, precipitated aluminas, aluminum metal, aluminum hydroxide,aluminum salts, alkali aluminates and alumina sols. Specific examples ofaluminum alkoxides include, but are not limited to aluminum orthosec-butoxide and aluminum ortho isopropoxide. Sources of M include butare not limited to zinc acetate, zinc chloride, cobalt acetate, cobaltchloride, magnesium acetate, magnesium nitrate, manganese sulfate,manganese acetate and manganese nitrate. Sources of phosphorus include,but are not limited to, orthophosphoric acid, phosphorus pentoxide andammonium dihydrogen phosphate. Sources of silica include but are notlimited to tetraethylorthosilicate, colloidal silica, alkali silicatesand precipitated silica. Sources of the other E elements include but arenot limited to precipitated gallium hydroxide, gallium chloride, galliumsulfate or gallium nitrate. Sources of the A metals include the halidesalts, nitrate salts, hydroxide salts, acetate salts, and sulfate saltsof the respective alkali metals. R is at least one of any organoammoniumcation selected from the groups consisting of quaternary ammonium,diquaternary ammonium, triquaternary ammonium, quatroquaternary ammoniumcations and mixtures thereof, a few examples of which, but not limitedto, are ethyltrimethylammonium (ETMA⁺), choline, diethydimethylammonium(DEDMA⁺), trimethylpropylammonium, tetramethylammonium (TMA⁺),tetraethylammonium (TEA⁺), tetrapropylammonium (TPA⁺), hexamethonium(HM²⁺), N,N,N′,N′-tetramethyl-N,N′-p-xyleno-1,6-hexanediammonium,N,N,N′,N′-tetramethyl-N,N′-butano-1,6-hexanediammonium,tris-1,3,5-(dimethylethylammoniomethyl)benzene,[(C₆H₅CH₂)(Me₂)N(—CH₂CH(OH)CH₂N(Me₂)-)₃CH₂C₆H₅]⁴⁺ and mixtures thereof,and the sources include the hydroxide, chloride, bromide, iodide,acetate and fluoride compounds. Specific examples include withoutlimitation ethyltrimethylammonium hydroxide, ethyltrimethylammoniumchloride, diethyldimethylammonium chloride, diethyldimethylammoniumhydroxide, propyltrimethylammonium chloride, tetramethylammoniumchloride, tetraethylammonium hydroxide, tetrapropylammonium hydroxide,hexamethonium dihydroxide, hexamethonium dichloride,N,N,N′,N′-tetramethyl-N,N′-p-xyleno-1,6-hexanediammonium dibromide,N,N,N′,N′-tetramethyl-N,N′-butano-1,6-hexanediammonium dihydroxide,tris-1,3,5-(dimethylethylammoniomethyl)benzene tribromide and[(C₆H₅CH₂)(Me₂)N(—CH₂CH(OH)CH₂N(Me₂)-)₃CH₂C₆H₅]⁴⁺ tetrachloride.

The reaction mixture containing reactive sources of the desiredcomponents can be described in terms of molar ratios of the oxides bythe formula:

aR_(2/p)O:bA₂O:cMO:E₂O₃ :dP₂O₅ :eSiO₂ :fH₂O

where “a” varies from about 2.1 to about 120, “b” varies from about 0.1to about 8, “c” varies from about 0.01 to about 8, “d” varies from about1.69 to about 30, “e” varies from 0.01 to 16 and “f” varies from 50 to5000. If alkoxides are used, it is preferred to include a distillationor evaporative step to remove the alcohol hydrolysis products. Thereaction mixture is now reacted at a temperature of about 60° C. toabout 200° C. and preferably from about 95° C. to about 175° C. for aperiod of about 1 day to about 3 weeks and preferably for a time ofabout 1 day to about 14 days in a sealed reaction vessel at autogenouspressure. After crystallization is complete, the solid product isisolated from the heterogeneous mixture by means such as filtration orcentrifugation, and then washed with deionized water and dried in air atambient temperature up to about 100° C. HCD MeAPSO seeds can optionallybe added to the reaction mixture in order to accelerate or otherwiseenhance the formation of the desired microporous composition.

A favored approach for the synthesis of HCD MeAP SOs is the ChargeDensity Mismatch Approach, which has been applied to the synthesis ofaluminosilicate zeolites (See U.S. Pat. No. 7,578,993 and CHEM. MATER.,2014, 26, 6684-6694). Metalloalumino(gallo)phosphosilicate solutions areprepared with excess phosphate and large, low charge density SDAs, suchas TPAOH, TEAOH, and TBAOH, which are then perturbed by the addition ofsmall amounts of alkali and more highly charged organoammonium cations,including quaternaryammonium, diquaternaryammonium, cyclicdiquaternaryammonium, triquaternaryammonium and quatroquaternaryammonium cations to induce crystallization under the synthesisconditions. This leads to rich chemistry in which there is oftencooperation between multiple SDAs to form a single molecular sievestructure. The method has advantages in expense and efficiency becausenon-commercially available organoammonium cations can be utilized insmall amounts as halide salts; they don't have to be converted to thehydroxide form for use, an additional and expensive step.

The various crystalline microporous HCDmetalloalumino(gallo)phosphosilicate species, which are obtained fromthe above-described process, are characterized by specific x-raydiffraction patterns, as illustrated in the examples.

The HCD MeAPSO may be modified in many ways to tailor it for use in aparticular application. Modifications include calcination, ammoniacalcinations, ion-exchange, steaming, various acid extractions, ammoniumhexafluorosilicate treatment, or any combination thereof, as outlinedfor the case of UZM-4 in U.S. Pat. No. 6,776,975 which is incorporatedby reference in its entirety. In addition, properties that may bemodified include porosity, adsorption, framework composition, acidity,thermal stability, ion-exchange capacity, etc.

As synthesized, the HCD MeAPSO material will contain some of theexchangeable or charge balancing cations in its pores. Theseexchangeable cations can be exchanged for other cations, or in the caseof organic cations, they can be removed by heating under controlledconditions. Sometimes, organic cations may be removed directly byion-exchange, heating may not be necessary. If heating is necessary toremove organic cations, a preferred method of their removal from thepores is ammonia calcination. Calcination in air converts the organiccations in the pores to protons, which can lead to the loss of somemetal, for example Al, from the framework upon exposure to ambientatmospheric water vapor. When the calcination is carried out in anammonia atmosphere, the organic cation in the pore is replaced by NH₄ ⁺cation and the framework remains intact (See STUDIES IN SURFACE SCIENCE,(2004) vol. 154, p. 1324-1331). Typical conditions for ammoniacalcinations include the use of gaseous anhydrous ammonia flowing at arate of 1.1 l/min while ramping the sample temperature at 5° C./min to500° C. and holding at that temperature for a time ranging from 5minutes to an hour. The resulting ammonium/alkali form of the HCD MeAPSOhas essentially the diffraction pattern of as-synthesized MeAPSO. Oncein this form, the ammonia calcined material may be ion-exchanged withH⁺, NH₄ ⁺, alkali metals, alkaline earth metals, transition metals, rareearth metals, or any mixture thereof, to achieve a wide variety ofcompositions with the HCD MeAPSO framework in superior condition.

When the HCD MeAPSO or its modified forms are calcined in air, there canbe a loss of metal from the framework, such as Al, which can alter thex-ray diffraction pattern from that observed for the as-synthesized HCDMeAPSO (See STUDIES IN SURFACE SCIENCE, (2004) vol. 154, p. 1324-1331).Typical conditions for the calcination of the HCD MeAPSO sample includeramping the temperature from room temperature to a calcinationtemperature of 400° to 600° C., preferably a calcination temperature of450° to 550° C. at a ramp rate of 1 to 5° C./min, preferably a ramp rateof 2 to 4° C./min, the temperature ramp conducted in an atmosphereconsisting either of flowing nitrogen or flowing clean dry air,preferably an atmosphere of flowing nitrogen. Once at the desiredcalcination temperature, if the calcination atmosphere employed duringthe temperature ramp is flowing clean dry air, it may remain flowingclean dry air. If the calcination atmosphere during the ramp was flowingnitrogen, it may remain flowing nitrogen at the calcination temperatureor it may be immediately converted to clean dry air; preferably at thecalcination temperature the calcination atmosphere will remain flowingnitrogen for a period of 1-10 hours and preferably for a period of 2-4hours before converting the calcination atmosphere to flowing clean dryair. The final step of the calcination is a dwell at the calcinationtemperature in clean dry air. Whether the calcination atmosphere duringthe initial temperature ramp was flowing nitrogen or flowing clean dryair, once at the calcination temperature and once the calcinationatmosphere is clean dry air, the HCD MeAPSO sample will spend a periodof 1-24 hours and preferably a period of 2-6 hours under theseconditions to complete the calcination process.

The crystalline HCD MeAPSO materials of this invention can be used forseparating mixtures of molecular species, removing contaminants throughion exchange and catalyzing various hydrocarbon conversion processes.Separation of molecular species can be based either on the molecularsize (kinetic diameter) or on the degree of polarity of the molecularspecies.

The HCD MeAPSO compositions of this invention can also be used as acatalyst or catalyst support in various hydrocarbon conversionprocesses. Hydrocarbon conversion processes are well known in the artand include cracking, hydrocracking, alkylation of both aromatics andisoparaffin, isomerization, polymerization, reforming, hydrogenation,dehydrogenation, transalkylation, dealkylation, hydration, dehydration,hydrotreating, hydrodenitrogenation, hydrodesulfurization, methanol toolefins, methanation and syngas shift process. Specific reactionconditions and the types of feeds which can be used in these processesare set forth in U.S. Pat. Nos. 4,310,440, 4,440,871 and 5,126,308,which are incorporated by reference. Preferred hydrocarbon conversionprocesses are those in which hydrogen is a component such ashydrotreating or hydrofining, hydrogenation, hydrocracking,hydrodenitrogenation, hydrodesulfurization, etc.

Hydrocracking conditions typically include a temperature in the range of400° to 1200° F. (204-649° C.), preferably between 600° and 950° F.(316-510° C.). Reaction pressures are in the range of atmospheric toabout 3,500 psig (24,132 kPa g), preferably between 200 and 3000 psig(1379-20,685 kPa g). Contact times usually correspond to liquid hourlyspace velocities (LHSV) in the range of about 0.1 hr⁻¹ to 15 hr⁻¹,preferably between about 0.2 and 3 hr⁻¹. Hydrogen circulation rates arein the range of 1,000 to 50,000 standard cubic feet (scf) per barrel ofcharge (178-8,888 std. m³/m³), preferably between 2,000 and 30,000 scfper barrel of charge (355-5,333 std. m³/m³). Suitable hydrotreatingconditions are generally within the broad ranges of hydrocrackingconditions set out above.

The reaction zone effluent is normally removed from the catalyst bed,subjected to partial condensation and vapor-liquid separation and thenfractionated to recover the various components thereof. The hydrogen,and if desired some or all of the unconverted heavier materials, arerecycled to the reactor. Alternatively, a two-stage flow may be employedwith the unconverted material being passed into a second reactor.Catalysts of the subject invention may be used in just one stage of sucha process or may be used in both reactor stages.

Catalytic cracking processes are preferably carried out with the HCDMeAPSO composition using feedstocks such as gas oils, heavy naphthas,deasphalted crude oil residua, etc. with gasoline being the principaldesired product. Temperature conditions of 850° to 1100° F. (455° C. to593° C.), LHSV values of 0.5 hr⁻¹ to 10 hr⁻¹ and pressure conditions offrom about 0 to 50 psig (0-345 kPa) are suitable.

Alkylation of aromatics usually involves reacting an aromatic (C₂ toC₁₂), especially benzene, with a monoolefin to produce a linear alkylsubstituted aromatic. The process is carried out at an aromatic: olefin(e.g., benzene:olefin) ratio of between 5:1 and 30:1, a LHSV of about0.3 to about 6 hr⁻¹, a temperature of about 100° to about 250° C. andpressures of about 200 to about 1000 psig (1,379-6,895 kPa). Furtherdetails on apparatus may be found in U.S. Pat. No. 4,870,222 which isincorporated by reference.

Alkylation of isoparaffins with olefins to produce alkylates suitable asmotor fuel components is carried out at temperatures of −30° to 40° C.,pressures from about atmospheric to about 6,894 kPa (1,000 psig) and aweight hourly space velocity (WHSV) of 0.1 hr⁻¹ to about 120 hr⁻¹.Details on paraffin alkylation may be found in U.S. Pat. Nos. 5,157,196and 5,157,197, which are incorporated by reference.

The conversion of methanol to olefins is effected by contacting themethanol with the HCD MeAPSO catalyst at conversion conditions, therebyforming the desired olefins. The methanol can be in the liquid or vaporphase with the vapor phase being preferred. Contacting the methanol withthe HCD MeAPSO catalyst can be done in a continuous mode or a batch modewith a continuous mode being preferred. The amount of time that themethanol is in contact with the HCD MeAPSO catalyst must be sufficientto convert the methanol to the desired light olefin products. When theprocess is carried out in a batch process, the contact time varies fromabout 0.001 hour to about 1 hour and preferably from about 0.01 hour toabout 1.0 hour. The longer contact times are used at lower temperatureswhile shorter times are used at higher temperatures. Further, when theprocess is carried out in a continuous mode, the Weight Hourly SpaceVelocity (WHSV) based on methanol can vary from about 1 hr⁻¹ to about1000 hr⁻¹ and preferably from about 1 hr⁻¹ to about 100 hr⁻¹.

Generally, the process must be carried out at elevated temperatures inorder to form light olefins at a fast enough rate. Thus, the processshould be carried out at a temperature of about 300° C. to about 600°C., preferably from about 400° C. to about 550° C. and most preferablyfrom about 450° C. to about 525° C. The process may be carried out overa wide range of pressure including autogenous pressure. Thus, thepressure can vary from about 0 kPa (0 psig) to about 1724 kPa (250 psig)and preferably from about 34 kPa (5 psig) to about 345 kPa (50 psig).

Optionally, the methanol feedstock may be diluted with an inert diluentin order to more efficiently convert the methanol to olefins. Examplesof the diluents which may be used are helium, argon, nitrogen, carbonmonoxide, carbon dioxide, hydrogen, steam, paraffinic hydrocarbons, e.g., methane, aromatic hydrocarbons, e. g., benzene, toluene and mixturesthereof. The amount of diluent used can vary considerably and is usuallyfrom about 5 to about 90 mole percent of the feedstock and preferablyfrom about 25 to about 75 mole percent.

The actual configuration of the reaction zone may be any well knowncatalyst reaction apparatus known in the art. Thus, a single reactionzone or a number of zones arranged in series or parallel may be used. Insuch reaction zones the methanol feedstock is flowed through a bedcontaining the HCD MeAPSO catalyst. When multiple reaction zones areused, one or more HCD MeAPSO catalysts may be used in series to producethe desired product mixture. Instead of a fixed bed, a dynamic bedsystem, e. g., fluidized or moving, may be used. Such a dynamic systemwould facilitate any regeneration of the HCD MeAPSO catalyst that may berequired. If regeneration is required, the HCD MeAPSO catalyst can becontinuously introduced as a moving bed to a regeneration zone where itcan be regenerated by means such as oxidation in an oxygen containingatmosphere to remove carbonaceous materials.

The following examples are presented in illustration of this inventionand are not intended as undue limitations on the generally broad scopeof the invention as set out in the appended claims. The HCD MeAPSOproducts will be designated with a name like MeAPSO-82 where the MeAPSOprefix indicates the material contains Me²⁺, E, Si, and P frameworkT-atoms while the suffix “−82” indicates the “−82” structure (whichhappens to have the CGS topology). In each case, the topology associatedwith the suffix “structure number” will be identified if known.

The structure of the HCD MeAPSO compositions of this invention wasdetermined by x-ray analysis. The x-ray patterns presented in thefollowing examples were obtained using standard x-ray powder diffractiontechniques. The radiation source was a high-intensity, x-ray tubeoperated at 45 kV and 35 mA. The diffraction pattern from the copperK-alpha radiation was obtained by appropriate computer based techniques.Flat compressed powder samples were continuously scanned at 2° to 56°(2θ). Interplanar spacings (d) in Angstrom units were obtained from theposition of the diffraction peaks expressed as θ where θ is the Braggangle as observed from digitized data. Intensities were determined fromthe integrated area of diffraction peaks after subtracting background,“I_(o)” being the intensity of the strongest line or peak, and “I” beingthe intensity of each of the other peaks.

As will be understood by those skilled in the art the determination ofthe parameter 20 is subject to both human and mechanical error, which incombination can impose an uncertainty of about ±0.4° on each reportedvalue of 2θ. This uncertainty is, of course, also manifested in thereported values of the d-spacings, which are calculated from the 2θvalues. This imprecision is general throughout the art and is notsufficient to preclude the differentiation of the present crystallinematerials from each other and from the compositions of the prior art. Insome of the x-ray patterns reported, the relative intensities of thed-spacings are indicated by the notations vs, s, m, and w whichrepresent very strong, strong, medium, and weak, respectively. In termsof 100×I/I_(o), the above designations are defined as:

w=0-15;m=15-60: s=60-80 and vs=80-100

In certain instances the purity of a synthesized product may be assessedwith reference to its x-ray powder diffraction pattern. Thus, forexample, if a sample is stated to be pure, it is intended only that thex-ray pattern of the sample is free of lines attributable to crystallineimpurities, not that there are no amorphous materials present.

In order to more fully illustrate the invention, the following examplesare set forth. It is to be understood that the examples are only by wayof illustration and are not intended as an undue limitation on the broadscope of the invention as set forth in the appended claims.

Example 1

A Teflon bottle was charged with 116.00 g DEDMAOH (20%, SACHEM, Inc.)followed by the addition of 5.17 g tetraethylorthosilicate (TEOS, 98%,Sigma-Aldrich). A stir bar was added and the bottle was sealed. Thereaction mixture was stirred for 18 hours to hydrolyze TEOS and thentransferred to a Teflon beaker and placed under a high speed stirrer.Pre-ground aluminum isopropoxide (13.2% Al), 4.97 g, was added to thereaction mixture and dissolved with stirring, followed by the additionof 25.00 g de-ionized water. Then 16.69 g H₃PO₄ (85.7%) was addeddropwise to the stirring reaction mixture. Separately, 5.34 gZn(OAc)₂*2H₂O was dissolved in 25.00 g de-ionized water and thissolution was added dropwise over the course of three stages. Anothersolution was prepared by dissolving 1.19 g KOAc (99.4%) in 10.64 gde-ionized water, which was added to the reaction mixture intermittentlyin a dropwise fashion. The reaction mixture was homogenized furtherbefore it was distributed among 7 Teflon-lined autoclaves, which werequiescently digested at autogenous pressure at temperatures of 95, 125,150, and 175° C., for either 48 or 168 hours or both. The solid productswere isolated by centrifugation, washed with de-ionized water and driedat room temperature. The products isolated from all of the digestionswere identified as containing MeAPSO-82 with the CGS topology as themajor product by powder x-ray diffraction. However, the productsisolated from the 95° C./168 hours and 175° C./48 hours digestionsyielded MeAPSO-82 free of other diffraction lines. The representativediffraction lines for the product from the 175° C./48 hours digestionare shown in Table 1 below. Elemental analysis showed this product wascomposed of the elemental ratios Al/P=0.54, Zn/P=0.52, K/P=0.24,Si/P=0.52 and N/P=0.30, consistent with the stoichiometryDEDMA_(0.30)K_(0.24)Zn_(0.52)Al_(0.54)Si_(0.52)P.

TABLE 1 2-Θ d(Å) I/I₀(%) 8.13 10.86 vs 10.70 8.26 w 11.54 7.66 w 12.257.22 m 12.96 6.82 w 13.18 6.71 w 16.30 5.44 m 16.69 5.31 w 17.03 5.20 w19.10 4.64 m 19.42 4.57 w 21.22 4.18 w 21.58 4.12 w 21.98 4.04 w 22.573.94 w 22.88 3.88 w 23.21 3.83 w 23.54 3.78 w 23.90 3.72 w 24.14 3.68 w24.68 3.60 m, br 26.14 3.41 m 26.48 3.36 w 26.92 3.31 m 28.04 3.18 w28.66 3.11 m 29.06 3.07 m 30.14 2.96 w 30.46 2.93 w 31.12 2.87 w 31.502.84 m 32.90 2.72 w 33.34 2.69 w 34.14 2.62 m 35.00 2.56 m

Example 2

A Teflon bottle was charged with 102.35 g ETMAOH (20%, SACHEM, Inc.).Additionally, 5.17 g TEOS (98%) and a stir bar were added. The bottlewas sealed and the solution was stirred to hydrolyze the TEOS. Thesolution was then transferred to a Teflon beaker and placed under a highspeed stirrer. Pre-ground aluminum isopropoxide (13.2% Al), 4.97 g, wasadded and dissolved with stirring. Next, 16.69 g H₃PO₄(85.7%) was addedto the reaction mixture in a dropwise fashion. This was followed by theaddition of 37.00 g de-ionized water to the reaction mixture.Separately, 5.34 g Zn(OAc)₂*2H₂O was dissolved in 25.00 g de-ionizedwater and the resulting solution was added dropwise to the reactionmixture. Additionally, 1.19 g KOAc (99.4%) was dissolved in 9.50 gde-ionized water and added to the reaction mixture in a dropwisefashion. The reaction mixture was homogenized further before it wasdistributed among 7 Teflon-lined autoclaves, which were quiescentlydigested at autogenous pressure at temperatures of 95, 125, 150, and175° C., for either 88 or 188 hours or both. The solid products wereisolated by centrifugation, washed with de-ionized water and dried atroom temperature. The products isolated from all of the digestions wereidentified as containing MeAPSO-82 with the CGS topology as the majorproduct by powder x-ray diffraction. However, the product isolated fromthe 95° C./188 hours digestion yielded MeAPSO-82 that was nearly pure.The representative diffraction lines for the product from the 95° C./188hours digestion are shown in Table 2 below. Elemental analysis showedthis product was composed of the elemental ratios Al/P=0.56, Zn/P=0.52,K/P=0.25, Si/P=0.56 and N/P=0.32, consistent with the stoichiometryETMA_(0.32)K_(0.25)Zn_(0.52)Al_(0.56)Si_(0.56)P.

TABLE 2 2-Θ d(Å) I/I₀(%) 6.28 14.06 m*, br 8.24 10.73 vs 10.80 8.19 w11.60 7.62 m 12.44 7.11 m 13.08 6.77 w 13.26 6.67 w 16.48 5.38 s 16.855.26 w 17.20 5.15 w 19.20 4.62 s 19.45 4.56 m 19.58 4.53 m 20.61 4.31 w21.63 4.11 m 21.84 4.07 m 22.24 3.99 m 22.82 3.89 w 23.05 3.86 m 23.303.81 w 23.78 3.74 m 24.14 3.68 m 24.86 3.58 m, br 26.3 3.39 m 26.76 3.33m 27.28 3.27 m 29.00 3.08 m 29.40 3.04 m 30.44 2.93 m 30.78 2.90 w 31.562.83 m 31.88 2.81 m 33.26 2.69 w 33.80 2.65 w 34.30 2.61 m 35.08 2.56 m*impurity

Example 3

A Teflon beaker was charged with 150.00 g ETMAOH (SACHEM Inc., 20%), towhich 6.06 g TEOS (98%) was added and the mixture was stirred for 2hours with a high speed mixer. The solution was transferred to a sealedTeflon bottle and digested for 2 hours at 95° C. to hydrolyze the TEOS.The reaction mixture was transferred back to a Teflon beaker and 5.79 gof pre-ground aluminum isopropoxide (Sigma-Aldrich, 13.3% Al) was addedand dissolved with vigorous stirring. This was followed by the fastdropwise addition of 19.57 g H₃PO₄(85.7%). Separately, 6.26 gZn(OAc)₂*2H₂O was dissolved in 30.30 g de-ionized water. This solutionwas added to the reaction mixture in a dropwise fashion in four separatealiquots, stirring between each addition. A solution was prepared bydissolving 2.82 g KOAc (99.4%) in 30.30 g de-ionized water. Thissolution was added dropwise to the reaction mixture in three aliquotsand the reaction mixture was homogenized. The reaction mixture wasdistributed among 7 Teflon-lined autoclaves and digested quiescently atautogenous pressure at temperatures of 95, 125, 150, and 175° C., foreither 33 or 149 hours or both. The solid products were isolated bycentrifugation, washed with de-ionized water and dried at roomtemperature. All of the products were found to contain MeAPSO-83 withthe BPH topology by powder x-ray diffraction, except three of theproducts contained a slight impurity. The representative diffractionlines are shown in Table 3 below for the pure MeAPSO-83 product from the125° C./149 hours digestion. Scanning Electron Microscopy (SEM) showedthis product to consist of hexagonal plate crystals ranging from 0.2 to0.8μ across and about 0.015 to 0.15μ thick. Elemental analysis of thissame product showed it was composed of the elemental ratios Al/P=0.43,Zn/P=0.64, Si/P=0.096, K/P=0.39, and N/P=0.18, consistent with thestoichiometry ETMA_(0.18)K_(0.39)Zn_(0.64)Al_(0.43)PSi_(0.10).

TABLE 3 2-Θ d(Å) I/I₀(%) 6.68 13.22 vs 7.56 11.69 vs 13.10 6.75 m 13.396.61 m 14.72 6.01 w 15.38 5.76 m 18.76 4.73 m 20.10 4.41 m 21.18 4.19 m23.77 3.74 w 24.10 3.69 s 26.52 3.36 m 27.24 3.27 m 27.48 3.24 w 28.323.15 m 28.58 3.12 m 29.70 3.01 m 30.06 2.97 m 30.56 2.92 m 31.04 2.88 w31.30 2.86 w 33.38 2.68 m 33.84 2.65 m 35.14 2.55 w 35.82 2.51 w 36.112.49 w 36.46 2.46 w 38.08 2.36 w 38.88 2.31 w 39.68 2.27 w 40.84 2.21 w43.06 2.10 w 43.46 2.08 w 43.82 2.06 w 45.94 1.97 w 49.60 1.84 w

Example 4

A Teflon bottle was charged with 145.00 g DEDMAOH (SACHEM Inc., 20%). Astir bar and 5.17 g TEOS (98%) were added, the bottle sealed and stirredat room temperature for 18 hours to hydrolyze the TEOS. The reactionmixture was then transferred to a Teflon beaker and placed under a highspeed stirrer. Pre-ground aluminum isopropoxide (13.2% Al), 4.97 g, wasthen added and dissolved with stirring. This was followed by thedropwise addition of 16.69 g H₃PO₄ (85.7%). Separately, Zn(OAc)₂*2 H₂O,5.34 g, was dissolved in 25.00 g de-ionized water. This solution wasadded dropwise to the reaction mixture. Another solution was prepared bydissolving 1.19 g KOAc (99.4%) in 12.44 g de-ionized water. Thissolution was added dropwise in two steps with a stirring period inbetween. The final reaction mixture was homogenized for an additionalhour. The reaction mixture was distributed among 7 Teflon-linedautoclaves and digested at autogenous pressures at temperatures of 95°,125°, 150°, and 175° C., for either 48 or 167 hours or both. The solidproducts were isolated by centrifugation and washed with de-ionizedwater. With the exception of the product of the 95° C./177 hoursdigestion, all of the products were found to contain MeAPSO-83 with theBPH topology as the major product by powder x-ray diffraction, with the48 hours samples containing a minor impurity. The representativediffraction lines are shown in Table 4 below for the pure MeAPSO-83product from the 150° C./167 hours digestion. Scanning ElectronMicroscopy (SEM) showed this product to consist of hexagonal platecrystals ranging from 0.5 to 3μ across and about 0.1 to 1.0μ thick.Elemental analysis of the same product showed it is composed of thefollowing elemental ratios: Al/P=0.50, Zn/P=0.64, Si/P=0.61, K/P=0.32,and N/P=0.38, consistent with the stoichiometryDEDMA_(0.38)K_(0.32)Zn_(0.64)Al_(0.50)PSi_(0.61).

TABLE 4 2-Θ d(Å) I/I₀(%) 6.70 13.18 s 7.56 11.68 vs 10.09 8.76 w 13.106.75 w 13.38 6.61 w 14.72 6.01 w 15.38 5.76 m 16.55 5.35 w 18.76 4.73 m20.12 4.41 m 21.16 4.20 m 23.72 3.75 w 24.08 3.69 m 26.46 3.37 m 27.203.28 m 27.42 3.25 w 28.26 3.16 m 28.54 3.13 m 29.64 3.01 m 30.02 2.97 m30.52 2.93 m 31.00 2.88 w 31.25 2.86 w 33.30 2.69 m 33.78 2.65 m 35.062.56 w 35.73 2.51 w 36.37 2.47 w 38.00 2.37 w 39.62 2.27 w 39.94 2.26 w40.76 2.21 w 42.92 2.11 w 43.36 2.09 w 43.78 2.07 w 49.46 1.84 m

Example 5

A Teflon bottle was charged with 174.00 g DEDMAOH (20%), followed by theaddition of 5.17 g TEOS (98%) and a stirbar. The bottle was sealed andthe solution was stirred for 18 hours to hydrolyze the TEOS. Thereaction mixture was transferred to a Teflon beaker and placed under ahigh speed stirrer. Pre-ground aluminum isopropoxide (13.2% Al), 4.97 g,was added and dissolved with vigorous stirring. This was followed by thedropwise addition of 16.69 g H₃PO₄ (85.7%). Separately, 5.34 gZn(OAc)₂*2H₂O was dissolved in 25.00 g de-ionized water and theresulting solution was added to the reaction mixture in a dropwisefashion. While the reaction mixture continued to stir, 1.19 g KOAc(99.4%) was dissolved in 7.88 g de-ionized water. This solution wasadded dropwise and post-addition the reaction mixture was homogenizedfurther. The reaction mixture was distributed among 7 Teflon-linedautoclaves and digested at autogenous pressure at temperatures of 95°,125°, 150°, and 175° C., for either 48 or 168 hours or both. The solidproducts were isolated by centrifugation and washed with de-ionizedwater. The product of the 95° C./168 hour digestion was identified asMeAPSO-83 with the BPH topology by powder x-ray diffraction. Therepresentative diffraction lines are shown in Table 5 below for thisproduct. Scanning Electron Microscopy (SEM) showed crystals of thisMeAPSO-83 product to consist of hexagonal plates 0.1 to 3μ in diameterand from 0.015 to 0.8μ thick. Elemental analysis of the same productshowed it is composed of the following elemental ratios: Al/P=0.41,Zn/P=0.85, Si/P=0.10, K/P=0.34, and N/P=0.22, consistent with thestoichiometry DEDMA_(0.22)K_(0.34)Zn_(0.85)Al_(0.41)PSi_(0.10).

TABLE 5 2-Θ d(Å) I/I₀(%) 6.72 13.14 vs 7.58 11.66 m 10.10 8.75 w 13.126.74 w 13.41 6.60 w 14.74 6.01 w 15.40 5.75 m 16.55 5.35 w 18.76 4.73 m20.12 4.41 m 21.16 4.20 m 23.76 3.74 w 24.08 3.69 m 26.50 3.36 m 27.213.28 w 27.44 3.25 w 28.30 3.15 w 28.56 3.12 m 29.66 3.01 m 30.06 2.97 m30.52 2.93 m 30.99 2.88 w 33.34 2.69 w 33.82 2.65 m 35.12 2.55 w 35.742.51 w 36.07 2.49 w 36.42 2.46 w 38.00 2.37 w 39.62 2.27 w 39.98 2.25 w40.78 2.21 w 42.96 2.10 w 43.36 2.09 w 44.04 2.05 w 49.48 1.84 w

Specific Embodiments

While the following is described in conjunction with specificembodiments, it will be understood that this description is intended toillustrate and not limit the scope of the preceding description and theappended claims.

A first embodiment of the invention is a microporous crystallinemetalloalumino(gallo)phosphosilicate material having a three-dimensionalframework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻, [PO_(4/2)]⁺ and SiO_(4/2)tetrahedral units and an empirical composition in the as synthesizedform and on an anhydrous basis expressed by an empirical formula ofR^(p+) _(r)A⁺ _(m)M²⁺ _(w)E_(x)PSi_(y)O_(z) where R is at least one ofany quaternary ammonium cation, diquaternary ammonium cationtriquaternary ammonium cation, quatroquaternary ammonium cation andmixtures thereof, “r” is the mole ratio of R to P and has a value ofabout 0.04 to about 4.0, “p” is the weighted average valence of R andvaries from 1 to 4, A is an alkali metal selected from the groupconsisting of Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺ and mixtures thereof, “m” is themole ratio of A to P and varies from 0.04 to 4.0, M is a divalent metalselected from the group consisting of Zn, Co, Mg, Mn and mixturesthereof, “w” is the mole ratio of M to P and varies from 0.00268 to1.35, E is a trivalent element selected from the group consisting ofaluminum and gallium and mixtures thereof, “x” is the mole ratio of E toP and varies from 0.1 to 4.0, “y” is the mole ratio of Si to P andvaries from 0.008 to about 4.5, and “z” is the mole ratio of 0 to P andhas a value determined by the equation z=(m+p·r+2·w+3·x+5+4·y)/2 wherethe T-atom compositions for M(“w”), E(“x”), Si(“y”) and P(1) are furtherconstrained when expressed as the mole fraction composition M²⁺_(w′)Al_(x′)Si_(y′)P_(z′), where w′=w/(w+x+y+1), x′=x/(w+x+y 1),y′=y/(w+x+y+1), z′=1/(w+x+y+1) and w′+x′+y′+z′=1, such that the plot ofthe allowed values of w′, x′, y′ and z′ in a quaternary phase diagramconforms to a composition bound by the 8-vertex, 10-sided polyhedronshown in FIG. 1 consisting of the eight vertices whose coordinates aregiven in Table A:

TABLE A Vertex Coordinates of MeAPSO Polyhedron Vertex x′ (Al) w′(Me²⁺)z′(P) 1 0.18499 0.00105 0.14799 2 0.42061 0.00105 0.10515 3 0.496370.00105 0.12409 4 0.48968 0.00105 0.39174 5 0.39841 0.09960 0.49800 60.47801 0.11952 0.39841 7 0.04980 0.44821 0.49801 8 0.05976 0.537850.39841and defined by the plane equation/inequalities given in Table B:

TABLE B MeAPSO Compositions - Criteria for x′, w′ and z′ Plane VerticesPlane Equation/Inequalities 1, 2, 3, 4 w′ ≥ 0.001502 5, 6, 7, 8 x′ +w′ + z′ ≤ 0.996016 4, 5, 6 1.239*x′ + 0.065*w′ + 1.004*z′ ≤ 1 1, 4, 5x′ + 2.274*w′ − 1.25*z′ ≥ 0 1, 5, 7 18.471*x′ + 18.471*w′ − 16.463*z′ ≥1 1, 7, 8 4.599*x′ + 0.6046*w′ + 1.004*z′ ≥ 1 1, 2, 8 1.004*x′ −2.341*w′ + 5.519*z′ ≥ 1 2, 3, 8 x′ + 2.86*w′ − 4.00*z′ ≤ 0 3, 4, 610.009*x′ + 0.9653*w′ + 0.2502*z′ ≤ 5 3, 6, 8 2.212*x′ + 2.212*w′ −0.808*z′ ≤ 1and the crystalline microporous metalloalumino(gallo)phosphosilicatemolecular sieve is characterized by a specific x-ray diffractionpattern. An embodiment of the invention is one, any or all of priorembodiments in this paragraph up through the first embodiment in thisparagraph wherein in the metalloalumino(gallo)phosphosilicate material Eis aluminum. An embodiment of the invention is one, any or all of priorembodiments in this paragraph up through the first embodiment in thisparagraph wherein in the metalloalumino(gallo)phosphosilicate material Eis gallium. An embodiment of the invention is one, any or all of priorembodiments in this paragraph up through the first embodiment in thisparagraph wherein in the metalloalumino(gallo)phosphosilicate material Ris at least one quaternary ammonium cation selected from the groupconsisting of tetramethylammonium (TMA⁺), ethyltrimethylammonium(ETMA⁺), propyltrimethylammonium (PTMA⁺), isopropyltrimethylammonium,diethyldimethylammonium (DEDMA⁺), trimethylbutylammonium (TMBA⁺),methyltriethylammonium (MTEA⁺), propylethyldimethylammonium (PEDMA⁺),N,N-dimethylpiperidinium, N,N-dimethyl-3,5-dimethylpiperidinium,dipropyldimethylammonium (DPDMA⁺), diethylmethylpropylammonium,trimethylpentylammonium (TMPA⁺), dimethyldiisopropylammonium,tetraethylammonium (TEA⁺), hexyltrimethylammonium (HTMA⁺),methylethyldipropylammonium, triethylpropylammonium,dibutyldimethylammonium, benzyltrimethylammonium (BzTMA⁺),diethyldipropylammonium, octyltrimethylammonium, tetrapropylammonium(TPA⁺), decyltrimethylammonium, adamantyltrimethylammonium,methyltributylammonium, dodecyltrimethylammonium,hexadecyltrimethylammonium, tetrabutylammonium (TBA⁺) and mixturesthereof. An embodiment of the invention is one, any or all of priorembodiments in this paragraph up through the first embodiment in thisparagraph wherein in the metalloalumino(gallo)phosphosilicate material Ris at least one diquaternary ammonium cation selected from the groupconsisting of methylene-bis-(trimethylammonium),bis-1,2-(trimethylammonium)ethylene, bis-1,3(trimethylammonium)propane,bis-1,3-(trimethylammonium)-2-propanol,bis-1,4-(trimethylammonium)butane, bis-1,5-(trimethylammonium)pentane(i.e., pentamethonium), bis-1,6-(trimethylammonium)hexane (i.e.,hexamethonium, HM²⁺), bis-1,8-(trimethylammonium)octane,bis-1,10-(trimethylammonium)decane, bis-1,5-(triethylammonium)pentane(i.e., pentaethonium), bis-1,6-(triethylammonium)hexane (i.e.,hexaethonium), bis-α,α′-(dimethylethylammonium)-p-xylene,bis-α,α′-(dimethylethylammonium)-m-xylene,bis-α,α′-(dimethylethylammonium)-o-xylene,bis-1,5-(N-methylpiperidinum)pentane andbis-1,6-(N-methylpiperidinum)hexane,N,N,N′,N′-tetramethyl-N,N′-p-xyleno-1,6-hexanediammonium,N,N,N′,N′-tetramethyl-N,N′-butano-1,6-hexanediammonium,N,N,N′,N′-tetrmaethyl-N,N′-hexano-1,6-hexanediammonium,N,N,N′,N′-tetraethyl-N,N′-hexano-1,5-pentanediammonium,N,N,N′,N′-tetramethyl-N,N′-m-xyleno-1,6-hexanediammonium,N,N,N′,N′-tetramethyl-N,N′-o-xyleno-1,2-ethylenediammonium,N,N,N′,N′-tetramethyl-N,N′-butano-1,2-ethylenediammonium,N,N,N′,N′-tetramethyl-N,N′-hexano-1,2-ethylenediammonium and mixturesthereof. An embodiment of the invention is one, any or all of priorembodiments in this paragraph up through the first embodiment in thisparagraph wherein in the metalloalumino(gallo)phosphosilicate material Ris at least one triquaternary ammonium cation selected from the groupconsisting of tris-1,3,5-(triethylammoniomethyl)benzene,tris-1,3,5-(trimethylammoniomethyl)benzene,tris-1,3,5-(dimethylethylammoniomethyl)benzene and mixtures thereof. Anembodiment of the invention is one, any or all of prior embodiments inthis paragraph up through the first embodiment in this paragraph whereinin the metalloalumino(gallo)phosphosilicate material R is at least onequatroquaternary ammonium cation selected from the group consisting of[(C₆H₅CH₂)(Me₂)N(−CH₂CH(OH)CH₂N(Me₂)-)₃CH₂C₆H₅]⁴⁺ (i.e.,dibenzylquatroquat), tetrakis-1,2,4,5-(trimethylammoniomethyl)benzene,tetrakis-1,2,4,5-(triethylammoniomethyl)benzene,tetrakis-1,2,4,5-(dimethylethylammoniomethyl)benzene and mixturesthereof. An embodiment of the invention is one, any or all of priorembodiments in this paragraph up through the first embodiment in thisparagraph wherein a crystalline modified form of the crystallinemicroporous metalloalumino(gallo)phosphosilicate comprises athree-dimensional framework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻, [PO_(4/2)]⁺and SiO_(4/2) tetrahedral units and derived by modifying the crystallinemicroporous metalloalumino(gallo)phosphosilicate, the modificationsincluding calcination, ammonia calcinations, ion-exchange, steaming,various acid extractions, ammonium hexafluorosilicate treatment, or anycombination thereof.

A second embodiment of the invention is a method for preparing amicroporous crystalline metalloalumino(gallo)phosphosilicate materialhaving a three-dimensional framework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻,[PO_(4/2)]⁺ and SiO_(4/2) tetrahedral units and an empirical compositionin the as synthesized form and on an anhydrous basis expressed by anempirical formula of R^(p+) _(r)A⁺ _(m)M²⁺ _(w)E_(x)PSi_(y)O_(z) where Ris at least one of any quaternary ammonium cation, diquaternary ammoniumcation triquaternary ammonium cation, quatroquaternary ammonium cationand mixtures thereof, “r” is the mole ratio of R to P and has a value ofabout 0.04 to about 4.0, “p” is the weighted average valence of R andvaries from 1 to 4, A is an alkali metal selected from the groupconsisting of Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺ and mixtures thereof, “m” is themole ratio of A to P and varies from 0.04 to 4.0, M is a divalent metalselected from the group Zn, Co, Mg, Mn and mixtures thereof, “w” is themole ratio of M to P and varies from 0.00268 to 1.35, E is a trivalentelement selected from the group consisting of aluminum and gallium andmixtures thereof, “x” is the mole ratio of E to P and varies from 0.1 to4.0, “y” is the mole ratio of Si to P and varies from 0.008 to about4.5, and “z” is the mole ratio of 0 to P and has a value determined bythe equation z=(m+p−r+2−w+3−x+5+4−y)/2 where the T-atom compositions forM(“w”), E(“x”), Si(“y”) and P(1) are further constrained when expressedas the mole fraction composition M²⁺ _(w′)Al_(x′)Si_(y′)P_(z′), wherew′=w/(w+x+y+1), x′=x/(w+x+y+1), y′=y/(w+x+y+1), z′=1/(w+x+y+1) andw′+x′+y′+z′=1, such that the plot of the allowed values of w′, x′, y′and z′ in a quaternary phase diagram conforms to a composition bound bythe 8-vertex, 10-sided polyhedron shown in FIG. 1 consisting of theeight vertices whose coordinates are given in Table A:

TABLE A Vertex Coordinates of MeAPSO Polyhedron Vertex x′ (Al) w′(Me²⁺)z′(P) 1 0.18499 0.00105 0.14799 2 0.42061 0.00105 0.10515 3 0.496370.00105 0.12409 4 0.48968 0.00105 0.39174 5 0.39841 0.09960 0.49800 60.47801 0.11952 0.39841 7 0.04980 0.44821 0.49801 8 0.05976 0.537850.39841and defined by the plane equation/inequalities given in Table B:

TABLE B MeAPSO Compositions - Criteria for x′, w′ and z′ Plane VerticesPlane Equation/Inequalities 1, 2, 3, 4 w′ ≥ 0.001502 5, 6, 7, 8 x′ +w′ + z′ ≤ 0.996016 4, 5, 6 1.239*x′ + 0.065*w′ + 1.004*z′ ≤ 1 1, 4, 5x′ + 2.274*w′ − 1.25*z′ ≥ 0 1, 5, 7 18.471*x′ + 18.471*w′ − 16.463*z′ ≥1 1, 7, 8 4.599*x′ + 0.6046*w′ + 1.004*z′ ≥ 1 1, 2, 8 1.004*x′ −2.341*w′ + 5.519*z′ ≥ 1 2, 3, 8 x′ + 2.86*w′ − 4.00*z′ ≤ 0 3, 4, 610.009*x′ + 0.9653*w′ + 0.2502*z′ ≤ 5 3, 6, 8 2.212*x′ + 2.212*w′ −0.808*z′ ≤ 1and the crystalline microporous metalloalumino(gallo)phosphosilicatemolecular sieve is characterized by a specific x-ray diffractionpattern, the process comprising forming a reaction mixture containingreactive sources of R, A, E, P, M and Si, and heating the reactionmixture at a temperature of about 60° C. to about 200° C. for a timesufficient to form the metalloalumino(gallo)phosphosilicate molecularsieve, the reaction mixture having a composition expressed in terms ofmole ratios of the oxides of aR_(2/p)O bM₂O cMO E₂O₃ dP₂O₅ eSiO₂ fH₂Owhere “a” has a value of about 2.1 to about 120, “b” has a value ofabout 0.1 to about 8, “c” has a value of about 0.01 to about 8, “d” hasa value of about 1.69 to about 30, “e” has a value from 0.01 to about 16and “f” has a value from 50 to about 5000. An embodiment of theinvention is one, any or all of prior embodiments in this paragraph upthrough the second embodiment in this paragraph where the initialreaction mixture is a clear solution before digestion. An embodiment ofthe invention is one, any or all of prior embodiments in this paragraphup through the second embodiment in this paragraph where A is selectedfrom the group consisting of Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺ and mixturesthereof and the source of A is selected from the group consisting ofhalide salts, nitrate salts, acetate salts, sulfate salts, hydroxidesalts and mixtures thereof. An embodiment of the invention is one, anyor all of prior embodiments in this paragraph up through the secondembodiment in this paragraph where M is selected from the groupconsisting of Zn²⁺, Mn²⁺, Co²⁺ and Mg₂₊ and mixtures thereof and thesource of M is selected from the group consisting of halide salts,nitrate salts, acetate salts, sulfate salts and mixtures thereof. Anembodiment of the invention is one, any or all of prior embodiments inthis paragraph up through the second embodiment in this paragraph wherethe source of E is selected from the group consisting of aluminumisopropoxide, aluminum sec-butoxide, precipitated alumina, Al(OH)₃,alkali aluminate salts, aluminum metal, aluminum halide salts, aluminumsulfate salts, aluminum nitrate salts, precipitated galliumoxyhydroxide, gallium nitrate, gallium sulfate and mixtures thereof. Anembodiment of the invention is one, any or all of prior embodiments inthis paragraph up through the second embodiment in this paragraph wherethe silicon source is selected from the group consisting oftetraethylorthosilicate, silicon alkoxides, fumed silica, colloidalsilica, alkali silicate salts, precipitated silica and mixtures thereof.An embodiment of the invention is one, any or all of prior embodimentsin this paragraph up through the second embodiment in this paragraphwhere the reaction mixture is reacted at a temperature of about 95° C.to about 175° C. for a time of about 1 day to about 14 days. Anembodiment of the invention is one, any or all of prior embodiments inthis paragraph up through the second embodiment in this paragraph whereR is at least one quaternary ammonium cation selected from the group ofquaternary ammonium cations consisting of tetramethylammonium (TMA⁺),ethyltrimethylammonium (ETMA⁺), propyltrimethylammonium (PTMA⁺),isopropyltrimethylammonium, diethyldimethylammonium (DEDMA⁺),trimethylbutylammonium (TMBA⁺), methyltriethylammonium (MTEA⁺),propylethyldimethylammonium (PEDMA⁺), N,N-dimethylpiperidinium,N,N-dimethyl-3,5-dimethylpiperidinium, dipropyldimethylammonium(DPDMA⁺), diethylmethylpropylammonium, trimethylpentylammonium (TMPA⁺),dimethyldiisopropylammonium, tetraethylammonium (TEA⁺),hexyltrimethylammonium (HTMA⁺), methylethyldipropylammonium,triethylpropylammonium, dibutyldimethylammonium, benzyltrimethylammonium(BzTMA⁺), diethyldipropylammonium, octyltrimethylammonium,tetrapropylammonium (TPA⁺), decyltrimethylammonium,adamantyltrimethylammonium, methyltributylammonium,dodecyltrimethylammonium, hexadecyltrimethylammonium, tetrabutylammonium(TBA⁺), methylene-bis-(trimethylammonium),bis-1,2-(trimethylammonium)ethylene, bis-1,3(trimethylammonium)propane,bis-1,3-(trimethylammonium)-2-propanol,bis-1,4-(trimethylammonium)butane, bis-1,5-(trimethylammonium)pentane(i.e., pentamethonium), bis-1,6-(trimethylammonium)hexane (i.e.,hexamethonium, HM²⁺), bis-1,8-(trimethylammonium)octane,bis-1,10-(trimethylammonium)decane, bis-1,5-(triethylammonium)pentane(i.e., pentaethonium), bis-1,6-(triethylammonium)hexane (i.e.,hexaethonium), bis-α,α′-(dimethylethylammonium)-p-xylene,bis-α,α′-(dimethylethylammonium)-m-xylene,bis-α,α′-(dimethylethylammonium)-o-xylene,bis-1,5-(N-methylpiperidinum)pentane andbis-1,6-(N-methylpiperidinum)hexane,N,N,N′,N′-tetramethyl-N,N′-p-xyleno-1,6-hexanediammonium,N,N,N′,N′-tetramethyl-N,N′-butano-1,6-hexanediammonium,N,N,N′,N′-tetrmaethyl-N,N′-hexano-1,6-hexanediammonium,N,N,N′,N′-tetraethyl-N,N′-hexano-1,5-pentanediammonium,N,N,N′,N′-tetramethyl-N,N′-m-xyleno-1,6-hexanediammonium,N,N,N′,N′-tetramethyl-N,N′-o-xyleno-1,2-ethylenediammonium,N,N,N′,N′-tetramethyl-N,N′-butano-1,2-ethylenediammonium,N,N,N′,N′-tetramethyl-N,N′-hexano-1,2-ethylenediammonium,tris-1,3,5-(triethylammoniomethyl)benzene,tris-1,3,5-(trimethylammoniomethyl)benzene,tris-1,3,5-(dimethylethylammoniomethyl)benzene,[(C₆H₅CH₂)(Me₂)N(—CH₂CH(OH)CH₂N(Me₂)-)₃CH₂C₆H₅]⁴⁺ (i.e.,dibenzylquatroquat), tetrakis-1,2,4,5-(trimethylammoniomethyl)benzene,tetrakis-1,2,4,5-(triethylammoniomethyl)benzene,tetrakis-1,2,4,5-(dimethylethylammoniomethyl)benzene and mixturesthereof. An embodiment of the invention is one, any or all of priorembodiments in this paragraph up through the second embodiment in thisparagraph further comprising adding seeds of ametalloalumino(gallo)phosphosilicate material to the reaction mixture.

A third embodiment of the invention is a hydrocarbon conversion processcomprising contacting a hydrocarbon stream with a catalyst athydrocarbon conversion conditions to generate at least one convertedproduct, wherein the catalyst is selected from the group consisting of acrystalline microporous metalloalumino(gallo)phosphosilicate material, acrystalline microporous modified metalloalumino(gallo)phosphosilicatematerial and mixtures thereof, where themetalloalumino(gallo)phosphosilicate is a crystalline microporousmetalloalumino(gallo)phosphosilicate material having a three-dimensionalframework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻, [PO_(4/2)]⁺ and SiO_(4/2)tetrahedral units and an empirical composition in the as synthesizedform and on an anhydrous basis expressed by an empirical formula ofR^(p+) _(r)A⁺ _(m)M²⁺ _(w)E_(x)PSi_(y)O_(z) where R is at least one ofany quaternary ammonium cation, diquaternary ammonium cationtriquaternary ammonium cation, quatroquaternary ammonium cation andmixtures thereof, “r” is the mole ratio of R to P and has a value ofabout 0.04 to about 4.0, “p” is the weighted average valence of R andvaries from 1 to 4, A is an alkali metal selected from the groupconsisting of Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺ and mixtures thereof, “m” is themole ratio of A to P and varies from 0.04 to 4.0, M is a divalent metalselected from the group Zn, Co, Mg, Mn and mixtures thereof, “w” is themole ratio of M to P and varies from 0.00268 to 1.35, E is a trivalentelement selected from the group consisting of aluminum and gallium andmixtures thereof, “x” is the mole ratio of E to P and varies from 0.1 to4.0, “y” is the mole ratio of Si to P and varies from 0.008 to about4.5, and “z” is the mole ratio of 0 to P and has a value determined bythe equation z=(m+p−r+2−w+3−x+5+4−y)/2 where the T-atom compositions forM(“w”), E(“x”), Si(“y”) and P(1) are further constrained when expressedas the mole fraction composition M²⁺ _(w′)Al_(x′)Si_(y′)P_(z′), wherew′=w/(w+x+y+1), x′=x/(w+x+y+1), y′=y/(w+x+y+1), z′=1/(w+x+y+1) andw′+x′+y′+z′=1, such that the plot of the allowed values of w′, x′, y′and z′ in a quaternary phase diagram conforms to a composition bound bythe 8-vertex, 10-sided polyhedron shown in FIG. 1 consisting of theeight vertices whose coordinates are given in Table A:

TABLE A Vertex Coordinates of MeAPSO Polyhedron Vertex x′ (Al) w′(Me²⁺)z′(P) 1 0.18499 0.00105 0.14799 2 0.42061 0.00105 0.10515 3 0.496370.00105 0.12409 4 0.48968 0.00105 0.39174 5 0.39841 0.09960 0.49800 60.47801 0.11952 0.39841 7 0.04980 0.44821 0.49801 8 0.05976 0.537850.39841and defined by the plane equation/inequalities given in Table B:

TABLE B MeAPSO Compositions - Criteria for x′, w′ and z′ Plane VerticesPlane Equation/Inequalities 1, 2, 3, 4 w′ ≥ 0.001502 5, 6, 7, 8 x′ +w′ + z′ ≤ 0.996016 4, 5, 6 1.239*x′ + 0.065*w′ + 1.004*z′ ≤ 1 1, 4, 5x′ + 2.274*w′ − 1.25*z′ ≥ 0 1, 5, 7 18.471*x′ + 18.471*w′ − 16.463*z′ ≥1 1, 7, 8 4.599*x′ + 0.6046*w′ + 1.004*z′ ≥ 1 1, 2, 8 1.004*x′ −2.341*w′ + 5.519*z′ ≥ 1 2, 3, 8 x′ + 2.86*w′ − 4.00*z′ ≤ 0 3, 4, 610.009*x′ + 0.9653*w′ + 0.2502*z′ ≤ 5 3, 6, 8 2.212*x′ + 2.212*w′ −0.808*z′ ≤ 1and the crystalline microporous metalloalumino(gallo)phosphosilicatemolecular sieve is characterized by a specific x-ray diffractionpattern, and the crystalline microporous modifiedmetalloalumino(gallo)phosphosilicate consists of a three-dimensionalframework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻, [PO_(4/2)]⁺ and SiO_(4/2)tetrahedral units derived from the metalloalumino-(gallo)phosphosilicatevia the modification processes of calcination, ammonia calcinations,ion-exchange, steaming, various acid extractions, ammoniumhexafluorosilicate treatment, or any combination thereof. An embodimentof the invention is one, any or all of prior embodiments in thisparagraph up through the third embodiment in this paragraph wherein thehydrocarbon conversion process is selected from the group consisting ofcracking, hydrocracking, alkylation, isomerization, polymerization,reforming, hydrogenation, dehydrogenation, transalkylation,dealkylation, hydration, dehydration, hydrotreating, hydrofining,hydrodenitrogenation, hydrodesulfurization, methanol to olefins,methanation, syngas shift process, olefin dimerization, oligomerization,dewaxing, and combinations thereof.

Without further elaboration, it is believed that using the precedingdescription that one skilled in the art can utilize the presentinvention to its fullest extent and easily ascertain the essentialcharacteristics of this invention, without departing from the spirit andscope thereof, to make various changes and modifications of theinvention and to adapt it to various usages and conditions. Thepreceding preferred specific embodiments are, therefore, to be construedas merely illustrative, and not limiting the remainder of the disclosurein any way whatsoever, and that it is intended to cover variousmodifications and equivalent arrangements included within the scope ofthe appended claims.

In the foregoing, all temperatures are set forth in degrees Celsius and,all parts and percentages are by weight, unless otherwise indicated.

1. A method for preparing a microporous crystallinemetalloalumino(gallo)phosphosilicate material having a three-dimensionalframework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻, [PO_(4/2)]⁺ and SiO_(4/2)tetrahedral units and an empirical composition in the as synthesizedform and on an anhydrous basis expressed by an empirical formula of:R^(p+) _(r)A⁺ _(m)M²⁺ _(w)E_(x)PSi_(y)O_(z) where R is at least one ofany quaternary ammonium cation, diquaternary ammonium cationtriquaternary ammonium cation, quatroquaternary ammonium cation andmixtures thereof, “r” is the mole ratio of R to P and has a value ofabout 0.04 to about 4.0, “p” is the weighted average valence of R andvaries from 1 to 4, A is an alkali metal selected from the groupconsisting of Na⁺, K⁺, Rb⁺ and Cs⁺ and mixtures thereof, “m” is the moleratio of A to P and varies from 0.04 to 4.0, M is a divalent metalselected from the group Zn, Co, Mg, Mn and mixtures thereof, “w” is themole ratio of M to P and varies from 0.00268 to 1.35, E is a trivalentelement selected from the group consisting of aluminum and gallium andmixtures thereof, “x” is the mole ratio of E to P and varies from 0.1 to4.0, “y” is the mole ratio of Si to P and varies from 0.008 to about4.5, and “z” is the mole ratio of 0 to P and has a value determined bythe equation:z=(m+p·r+2·w+3·x+5+4·y)/2 where the T-atom compositions for M(“w”),E(“x”), Si(“y”) and P(1) are further constrained when expressed as themole fraction composition M²⁺ _(w′)Al_(x′)Si_(y′)P_(z′), wherew′=w/(w+x+y+1), x′=x/(w+x+y+1), y′=y/(w+x+y+1), z′=1/(w+x+y+1) andw′+x′+y′+z′=1, such that the plot of the allowed values of w′, x′, y′and z′ in a quaternary phase diagram conforms to a composition bound bythe 8-vertex, 10-sided polyhedron shown in FIG. 1 consisting of theeight vertices whose coordinates are given in Table A: TABLE A VertexCoordinates of MeAPSO Polyhedron Vertex x′ (Al) w′(Me²⁺) z′(P) 1 0.184990.00105 0.14799 2 0.42061 0.00105 0.10515 3 0.49637 0.00105 0.12409 40.48968 0.00105 0.39174 5 0.39841 0.09960 0.49800 6 0.47801 0.119520.39841 7 0.04980 0.44821 0.49801 8 0.05976 0.53785 0.39841

and defined by the plane equation/inequalities given in Table B: TABLE BMeAPSO Compositions - Criteria for x′, w′ and z′ Plane Vertices PlaneEquation/Inequalities 1, 2, 3, 4 w′ ≥ 0.001502 5, 6, 7, 8 x′ + w′ + z′ ≤0.996016 4, 5, 6 1.239*x′ + 0.065*w′ + 1.004*z′ ≤ 1 1, 4, 5 x′ +2.274*w′ − 1.25*z′ ≥ 0 1, 5, 7 18.471*x′ + 18.471*w′ − 16.463*z′ ≥ 1 1,7, 8 4.599*x′ + 0.6046*w′ + 1.004*z′ ≥ 1 1, 2, 8 1.004*x′ − 2.341*w′ +5.519*z′ ≥ 1 2, 3, 8 x′ + 2.86*w′ − 4.00*z′ ≤ 0 3, 4, 6 10.009*x′ +0.9653*w′ + 0.2502*z′ ≤ 5 3, 6, 8 2.212*x′ + 2.212*w′ − 0.808*z′ ≤ 1

and the crystalline microporous metalloalumino(gallo)phosphosilicatemolecular sieve is characterized by a specific x-ray diffractionpattern, the method comprising forming a reaction mixture containingreactive sources of R, A, E, P, M and Si, and heating the reactionmixture at a temperature of about 60° C. to about 200° C. for a timesufficient to form the metalloalumino(gallo)phosphosilicate molecularsieve, the reaction mixture having a composition expressed in terms ofmole ratios of the oxides of:aR_(2/p)O:bM₂O:cMO:E₂O₃ :dP₂O₅ :eSiO₂ :fH₂O where “a” has a value ofabout 2.1 to about 120, “b” has a value of about 0.1 to about 8, “c” hasa value of about 0.01 to about 8, “d” has a value of about 1.69 to about30, “e” has a value from 0.01 to about 16 and “f” has a value from 50 toabout
 5000. 2. The method of claim 1 where the initial reaction mixtureis a clear solution before digestion.
 3. The method of claim 1 where Ais selected from the group consisting of Li²⁺, Na²⁺, Mn²⁺, Rb²⁺ and Cs²⁺and mixtures thereof and the source of A is selected from the groupconsisting of halide salts, nitrate salts, acetate salts, sulfate salts,hydroxide salts and mixtures thereof.
 4. The method of claim 1 where Mis selected from the group consisting of Zn′, Co²⁺ and Mg²⁺ and mixturesthereof and the source of M is selected from the group consisting ofhalide salts, nitrate salts, acetate salts, sulfate salts and mixturesthereof.
 5. The method of claim 1 where the source of E is selected fromthe group consisting of aluminum isopropoxide, aluminum sec-butoxide,precipitated alumina, Al(OH)₃, alkali aluminate salts, aluminum metal,aluminum halide salts, aluminum sulfate salts, aluminum nitrate salts,precipitated gallium oxyhydroxide, gallium nitrate, gallium sulfate andmixtures thereof.
 6. The method of claim 1 where the silicon source isselected from the group consisting of tetraethylorthosilicate, siliconalkoxides, fumed silica, colloidal silica, alkali silicate salts,precipitated silica and mixtures thereof.
 7. The method of claim 1 wheresources of phosphorus are selected from orthophosphoric acid, phosphoruspentoxide and ammonium dihydrogen phosphate.
 8. The method of claim 1where the reaction mixture is reacted at a temperature of about 95° C.to about 175° C. for a time of about 1 day to about 14 days.
 9. Themethod of claim 1 where R is at least one quaternary ammonium cationselected from the group of quaternary ammonium cations consisting oftetramethylammonium (TMA⁺), ethyltrimethylammonium (ETMA⁺),propyltrimethylammonium (PTMA⁺), isopropyltrimethylammonium,diethyldimethylammonium (DEDMA⁺), trimethylbutylammonium (TMBA⁺),methyltriethylammonium (MTEA⁺), propylethyldimethylammonium (PEDMA⁺),N,N-dimethylpiperidinium, N,N-dimethyl-3,5-dimethylpiperidinium,dipropyldimethylammonium (DPDMA⁺), diethylmethylpropylammonium,trimethylpentylammonium (TMPA⁺), dimethyldiisopropylammonium,tetraethylammonium (TEA⁺), hexyltrimethylammonium (HTMA⁺),methylethyldipropylammonium, triethylpropylammonium,dibutyldimethylammonium, benzyltrimethylammonium (BzTMA⁺),diethyldipropylammonium, octyltrimethylammonium, tetrapropylammonium(TPA⁺), decyltrimethylammonium, adamantyltrimethylammonium,methyltributylammonium, dodecyltrimethylammonium,hexadecyltrimethylammonium, tetrabutylammonium (TBA⁺),methylene-bis-(trimethylammonium), bis-1,2-(trimethylammonium)ethylene,bis-1,3(trimethylammonium)propane,bis-1,3-(trimethylammonium)-2-propanol,bis-1,4-(trimethylammonium)butane, bis-1,5-(trimethylammonium)pentane(i.e., pentamethonium), bis-1,6-(trimethylammonium)hexane (i.e.,hexamethonium, HM²⁺), bis-1,8-(trimethylammonium)octane,bis-1,10-(trimethylammonium)decane, bis-1,5-(triethylammonium)pentane(i.e., pentaethonium), bis-1,6-(triethylammonium)hexane (i.e.,hexaethonium), bis-α,α′-(dimethylethylammonium)-p-xylene,bis-α,α′-(dimethylethylammonium)-m-xylene,bis-α,α′-(dimethylethylammonium)-o-xylene,bis-1,5-(N-methylpiperidinum)pentane andbis-1,6-(N-methylpiperidinum)hexane,N,N,N′,N′-tetramethyl-N,N′-p-xyleno-1,6-hexanediammonium,N,N,N′,N′-tetramethyl-N,N′-butano-1,6-hexanediammonium,N,N,N′,N′-tetrmaethyl-N,N′-hexano-1,6-hexanediammonium,N,N,N′,N′-tetraethyl-N,N′-hexano-1,5-pentanediammonium,N,N,N′,N′-tetramethyl-N,N′-m-xyleno-1,6-hexanediammonium,N,N,N′,N′-tetramethyl-N,N′-o-xyleno-1,2-ethylenediammonium,N,N,N′,N′-tetramethyl-N,N′-butano-1,2-ethylenediammonium,N,N,N′,N′-tetramethyl-N,N′-hexano-1,2-ethylenediammonium,tris-1,3,5-(triethylammoniomethyl)benzene,tris-1,3,5-(trimethylammoniomethyl)benzene,tris-1,3,5-(dimethylethylammoniomethyl)benzene,[(C₆H₅CH₂)(Me₂)N(—CH₂CH(OH)CH₂N(Me₂)-)₃CH₂C₆H₅]⁴⁺ (i.e.,dibenzylquatroquat), tetrakis-1,2,4,5-(trimethylammoniomethyl)benzene,tetrakis-1,2,4,5-(triethylammoniomethyl)benzene,tetrakis-1,2,4,5-(dimethylethylammoniomethyl)benzene and mixturesthereof.
 10. The method of claim 1 further comprising adding seeds of ametalloalumino(gallo)phosphosilicate material to the reaction mixture.11. The method of claim 1 further comprising a distillation orevaporative step to remove alcohol hydrolysis products when the sourceof silicon is an alkoxide.
 12. The method of claim 1 further comprisingcalcination, ammonia calcinations, ion-exchange, steaming, various acidextractions, ammonium hexafluorosilicate treatment or combinationsthereof.
 13. A hydrocarbon conversion process comprising contacting ahydrocarbon stream with a catalyst at hydrocarbon conversion conditionsto generate at least one converted product, wherein the catalyst isselected from the group consisting of a crystalline microporousmetalloalumino(gallo)phosphosilicate material, a crystalline microporousmodified metalloalumino(gallo)phosphosilicate material and mixturesthereof, where the metalloalumino(gallo)phosphosilicate is a crystallinemicroporous metalloalumino(gallo)phosphosilicate material having athree-dimensional framework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻, [PO_(4/2)]⁺and SiO_(4/2) tetrahedral units and an empirical composition in the assynthesized form and on an anhydrous basis expressed by an empiricalformula of:R^(p+) _(r)A⁺ _(m)M²⁺ _(w)E_(x)PSi_(y)O_(z) where R is at least one ofany quaternary ammonium cation, diquaternary ammonium cationtriquaternary ammonium cation, quatroquaternary ammonium cation andmixtures thereof, “r” is the mole ratio of R to P and has a value ofabout 0.04 to about 4.0, “p” is the weighted average valence of R andvaries from 1 to 4, A is an alkali metal selected from the groupconsisting of Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺ and mixtures thereof, “m” is themole ratio of A to P and varies from 0.04 to 4.0, M is a divalent metalselected from the group Zn, Co, Mg, Mn and mixtures thereof, “w” is themole ratio of M to P and varies from 0.00268 to 1.35, E is a trivalentelement selected from the group consisting of aluminum and gallium andmixtures thereof, “x” is the mole ratio of E to P and varies from 0.1 to4.0, “y” is the mole ratio of Si to P and varies from 0.008 to about4.5, and “z” is the mole ratio of 0 to P and has a value determined bythe equation:z=(m+p·r+2·w+3·x+5+4·y)/2 where the T-atom compositions for M(“w”),E(“x”), Si(“y”) and P(1) are further constrained when expressed as themole fraction composition M²⁺ _(w′)Al_(x′)Si_(y′)P_(z′), wherew′=w/(w+x+y+1), x′=x/(w+x+y+1), y′=y/(w+x+y+1), z′=1/(w+x+y+1) andw′+x′+y′+z′=1, such that the plot of the allowed values of w′, x′, y′and z′ in a quaternary phase diagram conforms to a composition bound bythe 8-vertex, 10-sided polyhedron shown in FIG. 1 consisting of theeight vertices whose coordinates are given in Table A: TABLE A VertexCoordinates of MeAPSO Polyhedron Vertex x′ (Al) w′(Me²⁺) z′(P) 1 0.184990.00105 0.14799 2 0.42061 0.00105 0.10515 3 0.49637 0.00105 0.12409 40.48968 0.00105 0.39174 5 0.39841 0.09960 0.49800 6 0.47801 0.119520.39841 7 0.04980 0.44821 0.49801 8 0.05976 0.53785 0.39841

and defined by the plane equation/inequalities given in Table B: TABLE BMeAPSO Compositions - Criteria for x′, w′ and z′ Plane Vertices PlaneEquation/Inequalities 1, 2, 3, 4 w′ ≥ 0.001502 5, 6, 7, 8 x′ + w′ + z′ ≤0.996016 4, 5, 6 1.239*x′ + 0.065*w′ + 1.004*z′ ≤ 1 1, 4, 5 x′ +2.274*w′ − 1.25*z′ ≥ 0 1, 5, 7 18.471*x′ + 18.471*w′ − 16.463*z′ ≥ 1 1,7, 8 4.599*x′ + 0.6046*w′ + 1.004*z′ ≥ 1 1, 2, 8 1.004*x′ − 2.341*w′ +5.519*z′ ≥ 1 2, 3, 8 x′ + 2.86*w′ − 4.00*z′ ≤ 0 3, 4, 6 10.009*x′ +0.9653*w′ + 0.2502*z′ ≤ 5 3, 6, 8 2.212*x′ + 2.212*w′ − 0.808*z′ ≤ 1

and the crystalline microporous metalloalumino(gallo)phosphosilicatemolecular sieve is characterized by a specific x-ray diffractionpattern, and the crystalline microporous modifiedmetalloalumino(gallo)phosphosilicate consists of a three-dimensionalframework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻, [PO_(4/2)]⁺ and SiO_(4/2)tetrahedral units derived from the metalloalumino-(gallo)phosphosilicateof claim 1 via the modification processes of calcination, ammoniacalcinations, ion-exchange, steaming, various acid extractions, ammoniumhexafluorosilicate treatment, or any combination thereof.
 14. Theprocess of claim 13 wherein the hydrocarbon conversion process isselected from the group consisting of cracking, hydrocracking,alkylation, isomerization, polymerization, reforming, hydrogenation,dehydrogenation, transalkylation, dealkylation, hydration, dehydration,hydrotreating, hydrofining, hydrodenitrogenation, hydrodesulfurization,methanol to olefins, methanation, syngas shift process, olefindimerization, oligomerization, dewaxing, and combinations thereof.